The recent discovery and successful large-area synthesis of graphene, with its unique physical properties, have led to a growing interest in its application for optoelectronic devices such as solar cells and light-emitting diodes. Because of its high transparency and electrical conductivity, chemical and mechanical robustness, as well as materials abundance, graphene is being explored as a potential replacement for indium tin oxide (ITO) as a transparent conducting electrode material. Simultaneously with the graphene development, single-crystalline semiconducting nanowires have been widely investigated due to their novel electrical and optical properties. In particular, nanowire-based hybrid photovoltaic (PV) structures have gained significant interest because of their potential to achieve efficient charge extraction via one-dimensional charge transport pathways and large interfacial area in well-ordered bulk heterojunction geometry. An effective interface between nanowires and graphene that maintains the advantages of each component is desirable.